Polymerization of olefins employing catalysts prepared from novel titanium compounds

ABSTRACT

Olefins are polymerized in the presence of catalysts prepared from titanium compounds prepared by reacting a titanium compound such as titanium tetraisopropoxide with a compound containing at least one aliphatic hydroxyl group.

BACKGROUND OF THE INVENTION

This invention relates to precursors for and to new catalystcompositions useful for initiating and promoting polymerization ofα-olefins and to a polymerization process employing such catalystcompositions.

It is well known that olefins such as ethylene, propylene and 1-butenein the presence of metallic catalysts, particularly the reactionproducts of organometallic compounds and transition metal compounds, canbe polymerized to form substantially linear backbone polymers ofrelatively high molecular weight. Typically such polymerizations arecarried out at relatively low temperatures and pressures.

Among the methods of producing such linear olefin polymers, some of themost widely utilized are those described by Professor Karl Ziegler inU.S. Pat. Nos. 3,113,115 and 3,257,332. In these methods, the catalystemployed is obtained by admixing a compound of a transition metal ofGroups IVB, VB, VIB, and VIII of Mendeleev's Periodic Table of Elementswith an organometallic compound. Generally, the halides, oxyhalides andalkoxides or esters of titanium, vanadium and zirconium are the mostwidely used transition metal compounds. Common examples of theorganometallic compounds include the hydrides, alkyls and haloalkyls ofaluminum, alkylaluminum halides, Grignard reagents, alkali metalaluminum hydrides, alkali metal borohydrides, alkali metal hydrides,alkaline earth metal hydrides and the like. Usually, polymerization iscarried out in a reaction medium comprising an inert organic liquid,e.g. an aliphatic hydrocarbon, and the aforementioned catalyst. One ormore olefins may be brought into contact with the reaction medium in anysuitable manner. A molecular weight regulator, which is normallyhydrogen, is usually present in the reaction vessel in order to suppressthe formation of undesirable high molecular weight polymers.

Following polymerization, it is common to remove catalyst residues fromthe polymer by repeatedly treating the polymer with alcohol or otherdeactivating agent such as aqueous base. Such catalyst deactivationand/or removal procedures are expensive both in time and materialconsumed as well as the equipment required to carry out such treatment.

Furthermore, most of the aforementioned known catalyst systems are moreefficient in preparing polyolefins in slurry (i.e., wherein the polymeris not dissolved in the carrier) than in solution (i.e., wherein thetemperature is high enough to solubilize the polymer in the carrier).The lower efficiencies of such catalysts in solution polymerization isbelieved to be caused by the general tendency of such catalysts tobecome rapidly depleted or deactivated by significantly highertemperatures that are normally employed in solution processes. Inaddition, processes involving the copolymerization of ethylene withhigher α-olefins exhibit catalyst efficiencies significantly lower thanethylene homopolymerization processes.

Recently, catalysts having higher efficiencies have been disclosed,e.g., U.S. Pat. Nos. 3,392,159; 3,737,393; West German PatentApplication No. 2,231,982 and British Pat. Nos. 1,305,610 and 1,358,437.While the increased efficiencies achieved by using these recentcatalysts are significant, even higher efficiencies are desirable,particularly in copolymerization processes.

Even more recently, e.g. British Pat. No. 1,492,379, high efficiencycatalysts have been employed which permit polymerization temperaturesabove 140° C. Such high polymerization temperatures provide for reducedenergy requirements in solution polymerization processes in that thecloser the polymerization temperature is to the boiling point of thepolymerization solvent, the less energy that is required in removing thesolvent.

The present invention provides for catalysts having higher efficienciesat these temperatures or higher polymerization temperatures atcomparable efficiencies.

SUMMARY OF THE INVENTION

One aspect of the present invention pertains to titanium complexesand/or compounds resulting from reacting

(A) at least one titanium compound represented by the formula Ti(OR)_(x)X_(4-x) wherein each R is independently a hydrocarbyl group having from1 to about 20, preferably from about 1 to about 10, most preferably fromabout 2 to about 4 carbon atoms; X is a halogen and x has a value fromzero to 4; with

(B) at least one compound containing at least one aliphatic hydroxylgroup represented by the formulas II and III;

wherein each A is independently a divalent hydrocarbyl group having from1 to about 10, preferably from 1 to about 4, carbon atoms; each R isindependently hydrogen, a hydrocarbyl group or a halogen, nitro orhydrocarbyloxy substituted hydrocarbyl group, each such hydrocarbyl orhydrocarbyloxy groups having from 1 to about 20, preferably from 1 toabout 10 carbon atoms; each R' is independently hydrogen, a halogenatom, a hydrocarbyl group, a hydrocarbyloxy group or a halogen, nitro orhydrocarbyloxy substituted hydrocarbyl group or a halogen, nitro orhydrocarbyloxy substituted hydrocarbyloxy group, each such hydrocarbylor hydrocarbyloxy groups having from 1 to about 20, preferably from 1 toabout 10 carbon atoms; each n is independently zero or 1; each n' has avalue of from 1 to 5, preferably from 1 to 2, and each x independentlyhas a value of from zero to 4; and wherein components (A) and (B) areemployed in quantities which provide a molar ratio of B:A of 0.1:1 toabout 10:1, preferably from about 1:1 to about 5:1, most preferably fromabout 1:1 to about 2:1.

Another aspect of the present invention concerns an improvement in aZiegler-Natta catalyst containing a titanium component and a metal alkylcomponent wherein the improvement comprises employing as the titaniumcomponent, that which results from reacting

(A) at least one titanium compound represented by the formula Ti(OR)_(x)X_(4-x) wherein each R is independently a hydrocarbyl group having from1 to about 20, preferably from 1 to about 10, most preferably from about2 to about 4 carbon atoms; X is a halogen and x has a value from zero to4; with

(B) at least one compound containing at least one aromatic hydroxylgroup represented by the formulas I, II, III or IV;

wherein each A is independently a divalent hydrocarbyl group having from1 to about 10, preferably from 1 to about 4, carbon atoms; each R isindependently hydrogen, a hydrocarbyl group or a halogen, nitro orhydrocarbyloxy substituted hydrocarbyl group, each such hydrocarbyl orhydrocarbyloxy groups having from 1 to about 20, preferably from 1 toabout 10 carbon atoms; each R' is independently hydrogen, a halogenatom, a hydrocarbyl group, a hydrocarbyloxy group or a halogen, nitro orhydrocarbyloxy substituted hydrocarbyl group or a halogen, nitro orhydrocarbyloxy substituted hydrocarbyloxy group, each such hydrocarbylor hydrocarbyloxy groups having from 1 to about 20, preferably from 1 toabout 10 carbon atoms; each n is independently zero or 1; each n' has avalue of from 1 to 5, preferably from 1 to 2, and each x independentlyhas a value of from zero to 4; and wherein components (A) and (B) areemployed in quantities which provide a molar ratio of B:A of 0.1:1 toabout 10:1, preferably from about 1:1 to about 5:1, most preferably fromabout 1:1 to about 2:1.

Also, another aspect of the present invention concerns a catalystcomposition resulting from reacting in an inert hydrocarbon medium

(A) at least one hydrocarbon soluble organomagnesium componentrepresented by the formula MgR"₂.xMR"_(y) wherein each R" isindependently a hydrocarbyl group having from 1 to 20 carbon atoms; M isa metal selected from Al, Zn, Si, Sn, B and P; y has a numbercorresponding to the valence of M and x has a value from about 0.001 toabout 10;

(B) a halide source selected from

(1) an active non-metallic halide, said non-metallic halidecorresponding to the formula R'X wherein R' is hydrogen or a hydrocarbylgroup having from 1 to about 20; preferably from 1 to about 10 carbonatoms and such that the hydrocarbyl halide is at least as active assec-butyl chloride and does not poison the catalyst and X is halogen; or

(2) a metallic halide corresponding to the formula MR_(y-a) X_(a)wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Tableof Elements, R is a monovalent hydrocarbyl group having from 1 to about20, preferably from 1 to about 10 carbon atoms, X is halogen, y is anumber corresponding to the valence of M and a is a number from 1 to y;

(C) a compound or complex resulting from reacting

(1) at least one titanium compound represented by the formula Ti(OR)_(x)X_(4-x) wherein each R is independently a hydrocarbyl group having from1 to about 20, preferably from about 1 to about 10, most preferably from2 to about 4, carbon atoms; X is a halogen and x has a value from zeroto 4; with

(2) at least one compound containing at least one aliphatic hydroxylgroup represented by the formulas I, II, III or IV ##STR1## wherein eachA is independently a divalent hydrocarbyl group having from 1 to about10, preferably from 1 to about 4, carbon atoms; each R is independentlyhydrogen, a hydrocarbyl group or a halogen, nitro or hydrocarbyloxysubstituted hydrocarbyl group, each such hydrocarbyl or hydrocarbyloxygroups having from 1 to about 20, preferably from 1 to about 10 carbonatoms; each R' is independently hydrogen, a halogen atom, a hydrocarbylgroup, a hydrocarbyloxy group or a halogen, nitro or hydrocarbyloxysubstituted hydrocarbyl group or a halogen, nitro or hydrocarbyloxysubstituted hydrocarbyloxy group, each such hydrocarbyl orhydrocarbyloxy groups having from 1 to about 20, preferably from 1 toabout 10 carbon atoms; each n is independently zero or 1; each n' has avalue of from 1 to 5, preferably from 1 to 2, and each x independentlyhas a value of from zero to 4; and wherein components (A) and (B) areemployed in quantities which provide a molar ratio of B:A of 0.1:1 toabout 10:1, preferably from about 1:1 to about 5:1, most preferably fromabout 1:1 to about 2:1;

and when components (A) and/or (B) do not contain or contain aninsufficient quantity of aluminum, then

(D) an aluminum compound represented by the formula AlR_(y') X_(y")wherein R is a hydrocarbyl group having from 1 to about 10, preferablyfrom 1 to about 4, carbon atoms; X is halogen and y' and y" each have avalue of from zero to three with the sum of y' and y" being three isemployed;

and wherein the components are employed in quantities so as to providethe following ratios:

(1) a Mg:Ti atomic ratio of from about 1:1 to about 200:1, preferablyfrom about 2:1 to about 100:1, most preferably from about 5:1 to about50:1;

(2) components (C-2) and (C-1) are employed in quantities which providea molar ratio of (C-2):(C-1) of from about 0.1:1 to about 10:1,preferably from about 1:1 to about 4:1, most preferably from about 1:1to about 2:1;

(3) excess X:Al ratio of from about 0.0005:1 to about 10:1, preferablyfrom about 0.002:1 to about 2:1, most preferably from about 0.01:1 toabout 1.4:1; and

(4) an Al:Ti atomic ratio of from about 0.1:1 to about 2000:1,preferably from about 0.5:1 to about 200:1, most preferably from about1:1 to about 75:1.

The excess X is the quantity of halide above that which would betheoretically required to convert the magnesium compound to thedihalide.

Still another aspect of the present invention pertains to bidentateligand-containing titanium compounds or complexes represented by theformulas ##STR2## wherein A and R are as previously defined; each Z isindependently a halogen or an R² O-group wherein each R² isindependently a hydrocarbyl group having from 1 to about 20, preferablyfrom 1 to about 10, most preferably from 2 to about 4, carbon atoms; z'has a value of 1 or 2; z has value of 3 when z' has a value of 1 and zhas a value of 2 when z' has a value of 2; ##STR3## wherein A, R', Z,and x are as previously defined; m' has a value of 1 or 2; m has a valueof 2 when m' has a value of 1 and m has a value of zero when m' has avalue of 2.

Another aspect of the present invention is a process for thepolymerization of α-olefins in the presence of the aforementionedcatalysts.

As employed herein, the terms hydrocarbyl and hydrocarbyloxy include,for example, alkyl, cycloalkyl, aryl, aralkyl, alkenyl, alkoxy,cycloalkoxyl, aryloxy, aralkyloxy, alkenyloxy and the like.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Suitable compounds containing at least one aliphatic hydroxyl groupwhich can be employed herein includes, for example, 1,2-dihydroxyoctane,d,l-benzoin, 1,2-benzenedimethanol, cis-1,2-cyclohexanedimethanol,1,2-butanediol, 1,3-dihydroxypropane, mixtures thereof and the like.

Particularly suitable titanium compounds which can be employed hereininclude for example, tetraethoxy titanium, tetraisopropoxy titanium,tetra-n-butoxy titanium, tetraphenoxy titanium, tetra-n-propoxytitanium, tetra-(2-ethylhexoxy)titanium, di-n-butoxy titaniumdichloride, titanium tetrachloride, mixtures thereof and the like.

Particularly suitable organomagnesium compounds include, for example,hydrocarbon soluble dihydrocarbylmagnesium such as the magnesiumdialkyls and the magnesium diaryls. Exemplary suitable magnesiumdialkyls include particularly n-butyl-sec-butyl magnesium, diisopropylmagnesium, di-n-hexyl magnesium, isopropyl-n-butyl magnesium,ethyl-n-hexyl magnesium, ethyl-n-butyl magnesium, di-n-octyl magnesiumand others wherein the alkyl has from 1 to 20 carbon atoms. Exemplarysuitable magnesium diaryls include diphenylmagnesium, dibenzylmagnesium,and ditolylmagnesium. Suitable organomagnesium compounds include alkyland aryl magnesium alkoxides and aryloxides and aryl and alkyl magnesiumhalides with the halogen-free organomagnesium compounds being moredesirable.

Among the halide sources which can be employed herein are the activenon-metallic halides and metallic halides.

Suitable non-metallic halides are represented by the formula R'X whereinR' is hydrogen or an active monovalent organic radical and X is ahalogen. Particularly suitable non-metallic halides include, forexample, hydrogen halides and active organic halides such as t-alkylhalides, allyl halides, benzyl halides and other active hydrocarbylhalides wherein hydrocarbyl is as defined hereinbefore. By an activeorganic halide is meant a hydrocarbyl halide that contains a labilehalogen at least as active, i.e., as easily lost to another compound, asthe halogen of sec-butyl chloride, preferably as active as t-butylchloride. In addition to the organic monohalides, it is understood thatorganic dihalides, trihalides and other polyhalides that are active asdefined hereinbefore are also suitably employed. Examples of preferredactive non-metallic halides include hydrogen chloride, hydrogen bromide,t-butyl chloride, t-amyl bromide, allyl chloride, benzyl chloride,crotyl chloride, methylvinyl carbinyl chloride, α-phenylethyl bromide,diphenyl methyl chloride and the like. Most preferred are hydrogenchloride, t-butyl chloride, allyl chloride and benzyl chloride.

Suitable metallic halides which can be employed herein include thoserepresented by the formula MR_(y-a) X_(a) wherein M is a metal of GroupsIIB, IIIA or IVA, of Mendeleev's Periodic Table of Elements, R is amonovalent organic radical, X is a halogen, Y has a value correspondingto the valence of M and a has a value from 1 to y. Preferred metallichalides are aluminum halides of the formula AlR_(3-a) X_(a) wherein eachR is independently hydrocarbyl as hereinbefore defined such as alkyl, Xis a halogen and a is a number from 1 to 3. Most preferred arealkylaluminum halides such as ethylaluminum sesquichloride,diethylaluminum chloride, ethylaluminum dichloride, and diethylaluminumbromide, with ethylaluminum dichloride being especially preferred.Alternatively, a metal halide such as aluminum trichloride or acombination of aluminum trichloride with an alkyl aluminum halide or atrialkyl aluminum compound may be suitable employed.

It is understood that the organic moieties of the aforementionedorganomagnesium, e.g., R", and the organic moieties of the halidesource, e.g., R and R', are suitably any other organic radical providedthat they do not contain functional groups that poison conventionalZiegler catalysts.

The magnesium halide can be preformed from the organomagnesium compoundand the halide source or it can be formed insitu in which instance thecatalyst is preferably prepared by mixing in a suitable solvent orreaction medium (1) the organomagnesium component and (2) the halidesource, followed by the other catalyst components.

The compound or complex formed from reacting said titanium component andsaid component having at least one aliphatic hydroxyl group per moleculecan be utilized as formed or the product can be isolated and thenutilized at the appropriate place in the catalyst preparation.

When it is desired to prepare complexes employing molar ratios oftitanium compound to hydroxyl-containing compound of about 1 to 1, it ispreferred to add the hydroxyl-containing compound to the titaniumcompound.

When it is desired to prepare complexes employing molar ratios oftitanium compound to hydroxyl-containing compound of about 1 to 2, it ispreferred to add the titanium compound to the hydroxyl-containingcompound.

Regardless of the molar ratios employed, when it is desired to prepare acomplex containing mixed ligands by employing differenthydroxyl-containing compounds, it is preferred to add thehydroxyl-containing compounds to the titanium compound wherein the mostacidic hydroxyl-containing compound is added first.

When the titanium compound and aliphatic hydroxyl-containing compoundsare prereacted, temperatures from about 0° C. to about 200° C.,preferably from about 20° C. to about 100° C., can be employed.

The foregoing catalyst components are combined in proportions sufficientto provide atomic ratios as previously mentioned.

In cases wherein neither the organomagnesium component nor the halidesource contains aluminum or contains an insufficient quantity ofaluminum, it is necessary to include in the total catalyst an aluminumcompound such as an alkyl aluminum compound, e.g., a trialkyl aluminum,an alkyl aluminum halide or an aluminum halide. If polymerizationtemperatures below 180° C. are employed, the atomic ratios of Al:Ti maybe from about 0.1:1 to about 2000:1, preferably from 1:1 to about 200:1.However, when polymerization temperatures above 180° C. are employed,the aluminum compound is used in proportions such that the Al:Ti ratiois less than 120:1, preferably less than 50:1. It is understood,however, that the use of very low amounts of aluminum necessitates theuse of high purity solvents or diluents in the polymerization zone.Further, other components present in the zone should be essentially freeof impurities which react with aluminum alkyls. Otherwise, additionalquantities of an organometallic compound as previously described,preferably an organoaluminum compound, must be used to react with suchimpurities. Moreover, it is understood that in the catalyst the aluminumcompound should be in the form of trialkyl aluminum or alkyl aluminumhalide provided that the alkyl aluminum halide be substantially free ofalkyl aluminum dihalide. In the above mentioned aluminum compounds, thealkyl groups independently have from 1 to about 20, preferably from 1 toabout 10 carbon atoms.

When additional quantities of aluminum compound are employed, it can beadded to the aforementioned catalyst during the preparation thereof orthe aluminum deficient catalyst can be mixed with the appropriatealuminum compound prior to entry into the polymerization reactor or,alternatively, the aluminum deficient catalyst and the aluminum compoundcan be added to the polymerization reactor as separate streams oradditions.

The foregoing catalytic reaction is preferably carried out in thepresence of an inert diluent. The concentrations of catalyst componentsare preferably such that when the essential components of the catalyticreaction product are combined, the resultant slurry is from about 0.005to about 1.0 molar (moles/liter) with respect to magnesium. By way of anexample of suitable inert organic diluents can be mentioned liquifiedethane, propane, isobutane, n-butane, n-hexane, the various isomerichexanes, isooctane, paraffinic mixtures of alkanes having from 8 to 12carbon atoms, cyclohexane, methylcyclopentane, dimethylcyclohexane,dodecane, industrial solvents composed of saturated or aromatichydrocarbons such as kerosene, naphthas, etc., especially when free ofany olefin compounds and other impurities, and especially those havingboiling points in the range from about -50° to about 200° C. Alsoincluded as suitable inert diluents are benzene, toluene, ethylbenzene,cumene, decalin and the like.

Mixing of the catalyst components to provide the desired catalyticreaction product is advantageously carried out under an inert atmospheresuch as nitrogen, argon or other inert gas at temperatures in the rangefrom about -100° to about 200° C., preferably from about 0° to about100° C. The period of mixing is not considered to be critical as it isfound that a sufficient catalyst composition most often occurs withinabout 1 minute or less. In the preparation of the catalytic reactionproduct, it is not necessary to separate hydrocarbon soluble componentsfrom hydrocarbon insoluble components of the reaction product.

While the catalysts can be prepared by adding the components inessentially any order, it is preferred to add the components in one ofthe following orders:

(1) A, B, ((C-1) and (C-2), prereacted), D (if required)

(2) A, B, D (if required), ((C-1) and (C-2), prereacted)

(3) (A and B, prereacted), ((C-1) and (C-2), prereacted), D (ifrequired)

(4) (A and B, prereacted), D (if required), ((C-1) and (C-2),prereacted)

(5) (A, B and D, if required, prereacted), ((C-1) and (C-2), prereacted)

In the polymerization process employing the aforementioned catalyticreaction product, polymerization is effected by adding a catalyticamount of the above catalyst composition to a polymerization zonecontaining α-olefin monomer, or vice versa. Any polymerization methodcan be employed including slurry, solution, gas phase, high pressureprocess, and the like. The polymerization zone is usually maintained attemperatures in the range from about 0° to about 300° C., preferably atsolution polymerization temperatures, e.g., from about 130° to about250° C., for a residence time of about a few seconds to several days,preferably 15 seconds to 2 hours (7200 s). It is generally desirable tocarry out the polymerization in the absence of moisture and oxygen and acatalytic amount of the catalytic reaction product is generally withinthe range from about 0.0001 to about 0.1 millimoles titanium per literof diluent. It is understood, however, that the most advantageouscatalyst concentration will depend upon polymerization conditions suchas temperature, pressure, solvent and presence of catalyst poisons andthat the foregoing range is given to obtain maximum catalyst yields inweight of polymer per unit weight of titanium. Generally, in thepolymerization process, a carrier which may be an inert organic diluentor solvent or excess monomer is employed. In order to realize the fullbenefit of the high efficiency catalyst of the present invention, caremust be taken to avoid oversaturation of the solvent with polymer. Ifsuch saturation occurs before the catalyst becomes depleted, the fullefficiency of the catalyst is not realized. For best results, it ispreferred that the amount of polymer in the carrier not exceed about 50weight percent based on the total weight of the reaction mixture.

It is understood that inert diluents employed in the polymerizationrecipe are suitable as defined hereinbefore.

The polymerization pressures preferably employed are relatively low,e.g., from about 5 to about 10,000 psig (0.034-68.9 MPa), preferablyfrom about 50 to about 1000 psig, (0.345-6.89 MPa), most preferably fromabout 100 to about 700 psig (0.689-4.8 MPa). However, polymerizationwithin the scope of the present invention can occur at pressures fromatmospheric up to pressures determined by the capabilities of thepolymerization equipment, which can include pressures up to about 50,000psig (344.5 MPa). During polymerization it is desirable to stir thepolymerization recipe to obtain better temperature control and tomaintain uniform polymerization mixtures throughout the polymerizationzone.

In order to optimize catalyst yields in the polymerization of ethyleneunder solution conditions, it is preferable to maintain an ethyleneconcentration in the solvent in the range of from about 1 to about 10weight percent, most advantageously from about 1.2 to about 2 weightpercent. To achieve this, when an excess of ethylene is fed into thesystem, a portion of the ethylene can be vented. In other processes, itis preferred to conduct the polymerization in an excess of the α-olefinbeing polymerized in order to optimize catalyst yields.

Hydrogen can be employed in the practice of this invention to controlthe molecular weight of the resultant polymer. For the purpose of thisinvention, it is beneficial to employ hydrogen in concentrations rangingfrom about 0.001 to about 1 mole per mole of monomer. The larger amountsof hydrogen within this range are found to produce generally lowermolecular weight polymers. It is understood that hydrogen can be addedwith a monomer stream to the polymerization vessel or separately addedto the vessel before, during or after addition of the monomer to thepolymerization vessel, but during or before the addition of thecatalyst.

The monomer or mixture of monomers is contacted with the catalyticreaction product in any conventional manner, preferably by bringing thecatalytic reaction product and monomer together with intimate agitationprovided by suitable stirring or other means. Agitation can be continuedduring polymerization, or in some instances, the polymerization can beallowed to remain unstirred while the polymerization takes place. In thecase of more rapid reactions with more active catalysts, means can beprovided for refluxing monomer and solvent, if any of the latter ispresent, in order to remove the heat of reaction. In any event, adequatemeans should be provided for dissipating the exothermic heat ofpolymerization. If desired, the monomer can be brought in the vaporphase into contact with the catalytic reaction product, in the presenceor absence of liquid material. The polymerization can be effected in thebatch manner, or in a continuous manner, such as, for example, bypassing the reaction mixture through an elongaged reaction tube which iscontacted externally with suitable cooling media to maintain the desiredreaction temperature, or by passing the reaction mixture through anequilibrium overflow reactor or a series of the same.

The polymer is readily recovered from the polymerization mixture bydriving off unreacted monomer and solvent if any is employed. No furtherremoval of impurities is required. Thus, a significant advantage of thepresent invention is the elimination of the catalyst residue removalsteps. In some instances, however, it may be desirable to add a smallamount of a catalyst deactivating reagent of the types conventionallyemployed for deactivating Ziegler catalysts. The resultant polymer isfound to contain insignificant amounts of catalyst residue and topossess a relatively narrow molecular weight distribution.

The following examples are given to illustrate the invention, and shouldnot be construed as limiting its scope. All percentages are by weightand all parts are by molar or atomic ratio unless otherwise indicated.

In the following examples, the melt index values I₂ and I₁₀ weredetermined by ASTM D 1238-70 and the density values were determined byASTM D 1248.

EXAMPLES

The position of ring substituents employed herein are in accordance withthe Definitive Rules For Nomenclature of Organic Chemistry as providedin the Handbook of Chemistry and Physics, 50th Ed., Chemical Rubber Co.,page C-1 et seq.

PREPARATION OF COMPLEXES

The new titanium complexes were prepared by mixing stock solutions(0.015 molar) of the titanium source, titanium tetrachloride (TiCl₄) ortitanium tetraisopropoxide (tipt), and the aliphatic hydroxyl ligand inthe desired ratio at the indicated temperature. The ratio (L/M) of molesligand (L) to moles of titanium in the titanium source (M) utilized toprepare the desired complexes employed in the following examples isshown under the column heading L/M. However, in those instances wherethe titanium source was tipt and the L/M ratio was 2/1, then thesecomplexes were prepared, isolated and then redissolved in Isopar® E. Thevarious stock solutions were prepared at ambient temperatures bydiluting the titanium source and/or ligand with Isopar® E (anisoparaffinic hydrocarbon fraction having a boiling range of 116°-134°C.) to the desired volume to produce 0.015 molar solutions. These stocksolutions were stored under a nitrogen atmosphere to preventdecomposition.

Complexes were prepared by mixing at ambient conditions (˜25° C.) 1.0 or2.0 cc of the 0.015 m stock titanium source with the required amount ofstock ligand (0.015 m) solution to give the desired molar ligand tometal ratio (L/M). The mixture, usually colored, was allowed to sit forat least 5 minutes after which time it was added to the catalyst make upin place of the normal titanium source.

PREPARATION OF CATALYST COMPOSITIONS

Method A-1

The catalyst compositions were prepared by adding with stirring under anitrogen atmosphere to a 4-ounce (118.3 cc) serum bottle the followingcomponents in the indicated order.

    ______________________________________                                        42 - x cc of Isopar ® E                                                   4.0 cc    of 0.15 m di-butyl magnesium* (DBM)                                 4.0 cc    of 0.15 m ethyl aluminum dichloride (EADC)                          x cc      of titanium source or novel complex                                 50.0 cc   total                                                               ______________________________________                                         *Dibutylmagnesium is a commercial product of the Lithium Corporation of       America. Its composition is indicated to be predominately nbutyl-s-butyl      magnesium. Other commercially available magnesium alkyls that can be          utilized are manufactured by Texas Alkyls and marketed under the tradenam     Magala and, Schering AG and marketed under the tradename Bomag.          

All final catalyst solutions were 0.0003 molar in titanium and thevolume of catalyst normally injected for a polymerization run was 10 cc(0.003 mmoles Ti). The atomic ratio of Mg/Al/Cl/Ti for these catalystsare shown in the appropriate tables.

Method A-2

The catalyst compositions were prepared by the procedure of Method A-1from the following components added in the order indicated.

    ______________________________________                                        46 - x cc  of Isopar ® E                                                  2.0 cc     of 0.15 m DBM                                                      2.0 cc     of 0.15 m EADC                                                     x cc       of titanium source or novel complex                                50.0 cc    total                                                              ______________________________________                                    

All final catalyst solutions were 0.0003 molar in titanium and thevolume of catalyst normally injected for a polymerization run was 10 cc(0.003 mmoles Ti). The atomic ratio of Mg/Al/Cl/Ti for these catalystare shown in the appropriate tables.

Method A-3

The catalyst compositions were prepared by the procedure of Method A-1from the following components added in the order indicated.

    ______________________________________                                        50 - (2A + x) cc                                                                           of Isopar ® E                                                A cc         of 0.15 m DBM                                                    A cc         of 0.15 m EADC                                                   x cc         0.015 m Ti source or novel complex                               50.0 cc      total                                                            ______________________________________                                    

Method B

1. Preparation of Anhydrous MgCl₂

To 21.16 ml of 0.709 molar dibutyl magnesium was added 78.84 ml ofIsopar® E. Anhydrous electronic grade HCl was passed through thesolution until all of the magnesium alkyl had been converted tomagnesium chloride. Excess HCl was stripped from the slurry by purgingwith dry N₂. The resulting slurry (0.15 molar) of MgCl₂ in Isopar® E wasstored under a nitrogen atmosphere and utilized as a stock solution inthe preparation of catalyst compositions.

2. Catalyst Compositions

The catalyst compositions were prepared by adding with stirring under anitrogen atmosphere to a 4-ounce (118.3 cc) serum bottle the followingcomponents in the indicated order.

    ______________________________________                                        38 - x cc of Isopar ® E                                                   8.0 cc    of 0.15 m MgCl.sub.2 (as prepared above)                            2.0 cc    of 0.15 m diethyl aluminum chloride (DEAC)                                    as excess halide source                                             x cc      of titanium source or novel complex                                 2.0 cc    of 0.15 m triethyl aluminum (TEA)                                   50.0 cc   total                                                               ______________________________________                                    

All final catalyst solutions were 0.0003 molar in titanium and thevolume of catalyst normally injected for a polymerization run was 10 cc(0.003 millimoles Ti). The atomic ratios of Mg/Al/Cl/Ti for thesecatalysts were 40/20/90/1 if tetraisopropoxytitanium was employed as theTi precursor and 40/20/94/1 if tetrachlorotitanium was employed as theTi precursor.

3. Catalyst Compositions

The catalyst compositions were prepared by adding with stirring under anitrogen atmosphere to a 4-ounce (118.3 cc) serum bottle the followingcomponents in the indicated order.

    ______________________________________                                        45 - (x + y) cc                                                                            of Isopar ® E                                                4.0 cc       of 0.15 MgCl.sub.2                                               x cc         of 0.15 DEAC                                                     1.0 cc       of titanium source or novel complex                              y cc         of 0.15 m TEA                                                    50.0 cc      total                                                            ______________________________________                                    

All final catalyst solutions were 0.0003 molar in titanium and thevolume of catalyst normally injected for a polymerization run was 10 cc(0.003 millimoles). The final atomic ratios of Mg/Al/Cl/Ti are shown inthe appropriate Tables.

4. Catalyst Composition

The catalyst composition was prepared by adding with stirring under anitrogen atmosphere to a 4-ounce (118.3 cc) serum bottle the followingcomponents in the indicated order.

    ______________________________________                                                43.0 cc                                                                             of Isopar ® E                                                       4.0 cc                                                                              of 0.15 MgCl.sub.2                                                      0.5 cc                                                                              of 0.15 EADC                                                            1.0 cc                                                                              tetraisopropyltitanium                                                  1.5 cc                                                                              of 0.15 m TEA                                                           50.0 cc                                                                             total                                                           ______________________________________                                    

The final catalyst solution was 0.0003 molar in titanium and the volumeof catalyst normally injected for a polymerization run was 10 cc (0.003mmoles Ti). The atomic ratio of Mg/Al/Cl/Ti for this catalyst is shownin the appropriate tables.

POLYMERIZATION CONDITIONS General Procedure

A stirred, 1 gallon (3.79 l) batch reactor containing 2 liters ofIsopar® E was heated to the desired temperature and the solvent vaporpressure recorded. To this was added 5-6 psig (35-41 kPa) of hydrogenand the ethylene was added to give the desired final reactor pressure.An amount of the above catalyst was injected into the reactor and thereactor pressure was maintained constant at the desired final pressureby continually feeding ethylene during the polymerization run. The totalreaction time was 20 minutes (1200 s). The novel titanium species, theL/M ratio utilized in its preparation and the resulting catalystefficiencies are given in the following tables. All catalystefficiencies are given as grams of polyethylene produced per gram oftitanium employed in the 20 minutes (1200 s) polymerization run. Theinitial temperature was set at 195° C., the vapor pressure of thesolvent was 60 psig (414 kPa) and 5 psig (35 kPa) of hydrogen was addedfollowed by 385 psig (2655 kPa) of ethylene yielding a final totalpressure of 450 psig (3103 kPa).

Table I provides the results obtained when a hydroxyl-containingcompound represented by formula IX is employed as the ligand and TiCl₄was used as the Ti precursor.

The following formulas are referenced in the Tables. ##STR4##

                                      TABLE I                                     __________________________________________________________________________    Example.sup.1 or                                                                           Catalyst                 Ti                                      Comparative                                                                          Ti    Preparation              Eff. ×                                                                       Exotherm                           Experiment.sup.2                                                                     Compound                                                                            Method                                                                              Ligand Source   L/M                                                                              10.sup.-6                                                                          °C.                                                                          Mg/Al/Cl/Ti                  __________________________________________________________________________    1      TiCl.sub.4                                                                          A-1   Formula IX wherein                                                                            1/1                                                                              0.977                                                                              20    40/40/84/1                                      R.sub.a = R.sub.d = CH.sub.3 ; R.sub.b = R.sub.c = H                          and n = 0                                                  2      "     A-2   Formula IX wherein                                                                            1/1                                                                              0.850                                                                              17    20/20/44/1                                      R.sub.a = R.sub.d = CH.sub.3 ; R.sub.b = R.sub.c = H                          and n = 0                                                  3      "     A-1   Formula IX wherein                                                                            1/1                                                                              0.977                                                                              17    40/40/84/1                                      R.sub.a = R.sub.d = CH.sub.3 ; R.sub.b = R.sub.c = H;                         n = 2; and A = --CH.sub.2 --                               4      "     A-2   Formula IX wherein                                                                            1/1                                                                              0.838                                                                              16    20/20/44/1                                      R.sub.a = R.sub.d = CH.sub.3 ; R.sub.b = R.sub.c = H;                         n = 2; and A = --CH.sub.2 --                               5      "     A-1   Formula IX wherein                                                                            1/1                                                                              0.849                                                                              16    40/40/84/1                                      R.sub.a = R.sub.b = R.sub.c = H;                                              R.sub.d = C.sub.6 H.sub.13 and n = 0                       6      "     A-2   Formula IX wherein                                                                            1/1                                                                              0.874                                                                              18    20/20/44/1                                      R.sub.a = R.sub.b = R.sub.c = H;                                              R.sub.d = C.sub.6 H.sub.13 and n = 0                       A      "     B-3   --              -- 0.298                                                                               7    40/20/94/1                   __________________________________________________________________________

Table II provides the results obtained when a hydroxyl-containingcompound represented by selected hydroxyl compounds as the ligand andeither TiCl₄ or Tipt were used as Ti precursors.

                                      TABLE II                                    __________________________________________________________________________    Example.sup.1 or                                                                           Catalyst                  Ti                                     Comparative                                                                          Ti    Preparation               Eff. ×                                                                       Exotherm                          Experiment.sup.2                                                                     Compound                                                                            Method                                                                              Ligand           L/M                                                                              10.sup.-6                                                                          °C.                                                                          Mg/Al/Cl/Ti                 __________________________________________________________________________    7      TiCl.sub.4                                                                          A-1   Formula XI       1/1                                                                              0.892                                                                              21    40/40/84/1                  8      "     A-2    "               1/1                                                                              0.842                                                                              17    20/20/44/1                  9      "     A-1   Formula XIII     1/1                                                                              0.750                                                                              18    40/40/84/1                  10     "     A-2    "               1/1                                                                              0.569                                                                              11    20/20/44/1                  11     "     A-1   Formula XV wherein                                                                             1/1                                                                              0.738                                                                              16    40/40/84/1                                     R.sub.a = R.sub.b = H; R.sub.c = C.sub.6 H.sub.5 ;                            and n = 0                                                  B      "     B-4   --               -- 0.298                                                                              7     40/20/94/1                  12     "     A-1   Formula IX wherein                                                                             1/1                                                                              0.821                                                                              20    40/40/84/1                                     R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.5                                                                       and n = 0                                                  13     "     B-3   Formula IX wherein                                                                             1/1                                                                              1.111                                                                              20    40/10/84/1                               x = 0 R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 1 and n = 0                                                  14     TiCl.sub.4                                                                          B-3   Formula IX wherein                                                                             1/1                                                                              0.868                                                                              14    40/15/84/1                               x = 0 R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 1.5                                                                             and n = 0                                                  15     "     B-3   Formula IX wherein                                                                             1/1                                                                              0.925                                                                              15    40/5/84/1                                x = 0 R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 0.5                                                                             and n = 0                                                  16     "     B-3   Formula IX wherein                                                                             1/1                                                                              1.147                                                                              19    40/10/89/1                               x = 0.5                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A =  0.5                                                                            and n = 0                                                  17     "     B-3   Formula IX wherein                                                                             1/1                                                                              1.051                                                                              20    40/15/89/1                               x = 0.5                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 1.0                                                                             and n = 0                                                  18     "     B-3   Formula IX wherein                                                                             1/1                                                                              1.120                                                                              19    40/15/94/1                               x = 1.0                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 0.5                                                                             and n = 0                                                  19     "     B-3   Formula XI       "  1.073                                                                              18    40/10/84/1                               x = 0                                                                         A = 1.0                                                          20     "     B-3    "               1/1                                                                              0.976                                                                              15    40/5/84/1                                x = 0                                                                         A = 0.5                                                          21     "     B-3    "               1/1                                                                              0.938                                                                              16    40/15/84/1                               x = 0                                                                         A = 1.5                                                          22     "     B-3    "               1/1                                                                              1.232                                                                              20    40/10/89/1                               x = 0.5                                                                       A =  0.5                                                         23     "     B-3    "               1/1                                                                              1.091                                                                              20    40/15/89/1                               x = 0.5                                                                       A = 1.0                                                          24*    tipt  B-3   Formula IX wherein                                                                             2/1                                                                              0.639                                                                              11    40/40/105/1                              x = 2.5                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 1.5                                                                             and n = 0                                                  25*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.678                                                                              11    40/40/100/1                              x = 2.0                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 2.0                                                                             and n = 0                                                  26*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.667                                                                              13    40/35/100/1                              x = 2.0                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 1.5                                                                             and n = 0                                                  27*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.613                                                                              11    40/35/95/1                               x = 1.5                                                                             R.sub. a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                           H.sub.13                                                                A = 2.0                                                                             and n = 0                                                  28*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.622                                                                              10    40/35/90/1                               x = 1.0                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 2.5                                                                             and n = 0                                                  29*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.532                                                                              8     40/30/85/1                               x = 0.5                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 2.5                                                                             and n = 0                                                  30*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.600                                                                              11    40/30/90/1                               x = 1.0                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 2.0                                                                             and n = 0                                                  31*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.595                                                                              10    40/25/90/1                               x = 1.0                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 1.5                                                                             and n = 0                                                  32*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.586                                                                              10    40/20/90/1                               x = 1.0                                                                             R.sub.a = R.sub.b = R.sub.c = H; R.sub.d = C.sub.6                            H.sub.13                                                                A = 1.0                                                                             and n = 0                                                  C      "     B-4   --               -- 0.530                                                                              12    40/20/90/1                  33*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.683                                                                              14    40/20/90/1                               x = 1.0                                                                             R.sub.a = R.sub.d = --CH.sub.3 ; R.sub.b = R.sub.c = H                  A = 1.0                                                                             and n = 0                                                  34*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.632                                                                              13    40/25/90/1                               x = 1.0                                                                             R.sub.a = R.sub.d = --CH.sub.3 ; R.sub.b = R.sub. c =                         H                                                                       A = 1.5                                                                             and n = 0                                                  35*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.737                                                                              15    40/25/95/1                               x = 1.5                                                                             R.sub.a = R.sub.d = --CH.sub.3 ; R.sub.b = R.sub.c = H                  A = 1.0                                                                             and n = 0                                                  36*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.584                                                                              11    40/30/95/1                               x = 1.5                                                                             R.sub.a = R.sub.d = --CH.sub.3 ; R.sub.b = R.sub.c = H                  A = 1.5                                                                             and n = 0                                                  37*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.565                                                                              12    40/30/100/1                              x = 2.0                                                                             R.sub.a = R.sub.d = --CH.sub.3 ; R.sub.b = R.sub.c = H                  A = 1.0                                                                             and n = 0                                                  38*    "     B-3   Formula IX wherein                                                                             2/1                                                                              0.585                                                                              10    40/20/95/1                               x = 1.5                                                                             R.sub.a = R.sub.d  = --CH.sub.3 ; R.sub.b = R.sub.c =                         H                                                                       A = 0.5                                                                             and n = 0                                                  D      "     B-4   --               -- 0.575                                                                              13    40/20/90/1                  __________________________________________________________________________     *The titanium complexes in Examples 24-38 were prepared from the indicate     compounds, isolated and redissolved or dispersed in Isopar ® E.           .sup.1 The examples of the invention are designated by numerals.              .sup.2 Comparative experiments are designated by letters.                

EXAMPLES 39-44 Preparation and Recovery of Titanium Compounds orComplexes

To 50 ml of warm oxygen-free, dry toluene solution containing 0.01 molesof the hydroxyl-containing compound was added slowly, dropwise, 15 ml ofoxygen-free, dry toluene containing 0.005 moles of tetraisopropoxytitanium. No color change was observed. Heating, stirring and nitrogenblanket were maintained for 1 hour (3600 s) after which the solution wasallowed to come to room temperature. The total volume was then reducedto 5 ml by rotary evaporation after which white precipitates of thecomplexes or compounds were isolated. They were washed with cold dryoxygen-free toluene and dried overnight at room temperature undervacuum. The components and analytical results are given in Table III.

                                      TABLE III                                   __________________________________________________________________________         Hydroxyl-                        The complexes are believed              Example                                                                            Containing           Theoretical                                                                         Actual                                                                              to be represented                       No.  Material(s)       L/M                                                                              % C                                                                              % H                                                                              % C                                                                              % H                                                                              by the indicated formula                __________________________________________________________________________    39   Formula IX        2/1                                                                              57.1                                                                             9.59                                                                             56.4                                                                             9.84                                                                             X wherein n = 0; R.sub.a = R.sub.b                                            = R.sub.c = H;                               wherein R.sub.a = R.sub.b = R.sub.c = H;                                                                       and R.sub.d = C.sub.6 H.sub.13               R.sub.d = C.sub.6 H.sub.13 and n = 0                                     40   Formula IX        2/1                                                                              42.9                                                                             7.20                                                                             43.2                                                                             8.13                                                                             X wherein n = 0; R.sub.a = R.sub.c                                            = --CH.sub.3 ;                               wherein R.sub.a = R.sub.c = --CH.sub.3 ;                                                                       and R.sub.b = R.sub.d = H                    R.sub.b = R.sub.d = H and n = 0                                          41   Formula IX        2/1                                                                              58.4                                                                             5.20                                                                             58.7                                                                             4.79                                                                             X* wherein R.sub.a = R.sub.b =                                                R.sub.c = H;                                 wherein R.sub.a = R.sub.b = R.sub.c = H;                                                                       R.sub.d = C.sub.6 H.sub.5 and n =                                             0                                            R.sub.d = C.sub.6 H.sub.5 and n = 0                                      42   Formula XI        2/1                                                                              57.8                                                                             8.49                                                                             57.3                                                                             8.43                                                                             XIII                                    43   Formula XIII      2/1                                                                              60.0                                                                             5.04                                                                             59.8                                                                             5.08                                                                             XIV                                     44   Formula IX        2/1                                                                              36.8                                                                             6.17                                                                             36.9                                                                             6.04                                                                             X wherein R.sub.a = R.sub.b =                                                 R.sub.c = R.sub.d = H;                       wherein R.sub.a = R.sub.b = R.sub.c = R.sub.d = H;                                                             A = --CH.sub.2 -- and n = 1                  n = 1; A = --CH.sub.2 --                                                 __________________________________________________________________________     *isolated as the hemihydrate                                             

We claim:
 1. In a process for polymerizing at least one α-olefin or amixture of at least one α-olefin and at least one polymerizableethylenically unsaturated monomer in the presence of a supportedZiegler-Natta catalyst; the improvement which comprises employing as thetransition metal component of such catalyst that which results fromreacting(A) at least one titanium compound represented by the formulaTi(OR)_(x) X_(4-x) wherein each R is independently a hydrocarbyl grouphaving from 1 to about 20 carbon atoms; X is a halogen and x has a valuefrom zero to 4; with (B) at least one compound containing at least onealiphatic hydroxyl group represented by the formula ##STR5## wherein Ais a divalent hydrocarbyl group having from 1 to about 10 carbon atoms;each R is independently hydrogen, a hydrocarbyl group or a halogen,nitro or hydrocarbyloxy substituted hydrocarbyl group, each suchhydrocarbyl or hydrocarbyloxy groups having from 1 to about 20 carbonatoms; n is zero or 1; and wherein components (A) and (B) are employedin quantities which provide a molar ratio of (B):(A) of 0.1:1 to about10:1.
 2. A process of claim 1 wherein(1) in component (A)(a) each Rindependently has from 1 to about 10 carbon atoms; and (b) X ischlorine; (2) in component (B)(a) A has from 1 to about 4 carbon atoms;(b) when R is a hydroxyl substituted hydrocarbyl or a hydroxylsubstituted hydrocarbyloxy group, it has from 1 to about 10 carbonatoms; and (c) when R' is a hydrocarbyl group or a hydrocarbyloxy group,it has from about 1 to about 10 carbon atoms; (3) components (A) and (B)are employed in quantities which provides a molar ratio of B:A of fromabout 1:1 to about 5:1.
 3. A process of claim 2 wherein(a) in component(A), each R has from about 2 to about 4 carbon atoms; and (b) components(A) and (B) are employed in quantities which provide a molar ratio ofB:A of from about 1:1 to about 2:1.
 4. A process of claim 3 wherein(a) nhas a value of 1; (b) A is a methylene group; and (c) each R isindependently hydrogen, a methyl group or phenyl group.
 5. A process ofclaims 1, 2, 3 or 4 wherein component A is tetraisopropoxytitanium,tetra-n-butoxy titanium, titanium tetrachloride or a mixture thereof. 6.A process of claims 1, 2, 3 or 4 wherein ethylene or a mixture ofethylene and at least one α-olefin having from 2 to about 10 carbonatoms is polymerized.
 7. A process of claim 6 wherein ethylene or amixture of ethylene and at least one of butene-1, hexene-1 or octene-1is polymerized.
 8. A process of claim 5 wherein ethylene or a mixture ofethylene and at least one α-olefin having from 2 to about 10 carbonatoms is polymerized.
 9. A process of claim 8 wherein ethylene or amixture of ethylene and at least one of butene-1, hexene-1 or octene-1is polymerized.
 10. A process for polymerizing at least one α-olefin ora mixture of at least one α-olefin and at least one polymerizableethylenically unsaturated monomer under suitable polymerizationconditions in the presence of a catalyst composition resulting fromreacting in an inert hydrocarbon medium(A) at least one hydrocarbonsoluble organomagnesium component represented by the formulaMgR"₂.xMR"_(y) wherein each R" is independently a hydrocarbyl grouphaving from 1 to 20 carbon atoms; M is a metal selected from Al, Zn, Si,Sn, B and P; y has a number corresponding to the valence of M and x hasa value from about 0.001 to about 10; (B) a halide source selectedfrom(1) an active non-metallic halide, said non-metallic halidecorresponding to the formula R'X wherein R' is hydrogen or a hydrocarbylgroup having from 1 to about 20 carbon atoms and such that thehydrocarbyl halide is at least as active as sec-butyl chloride and doesnot poison the catalyst and X is halogen;or (2) a metallic halidecorresponding to the formula MR_(y-a) X_(a) wherein M is a metal ofGroup IIIA or IVA of Mendeleev's Periodic Table of Elements, R is amonovalent hydrocarbyl group having from 1 to about 20 carbon atoms, Xis halogen, Y is a number corresponding to the valence of M and a is anumber from 1 to y; and (C) a compound or complex resulting fromreacting(1) at least one titanium compound represented by the formulaTi(OR)_(x) X_(4-x) wherein each R is independently a hydrocarbyl grouphaving from 1 to about 20 carbon atoms; X is a halogen and x has a valuefrom zero to 4; with (2) at least one compound containing at least onealiphatic hydroxyl group represented by the formula ##STR6## whereineach A is a divalent hydrocarbyl group having from 1 to about 10 carbonatoms; each R is independently hydrogen, a hydrocarbyl group or ahalogen, nitro or hydrocarbyloxy substituted hydrocarbyl group, eachsuch hydrocarbyl or hydrocarbyloxy groups having from 1 to about 20carbon atoms; n is zero or 1;and when components (A) and/or (B) do notcontain or contain an insufficient quantity of aluminum, then (D) analuminum compound represented by the formula AlR_(y') X_(y") wherein Ris a hydrocarbyl group having from 1 to about 10 carbon atoms; X ishalogen and y' and y" each have a value of from zero to three with thesum of y' and y" being three is employed;and wherein the components areemployed in quantities so as to provide the following ratios: (1) aMg:Ti atomic ratio of from about 1:1 to about 200:1; (2) components(C-2) and (C-1) are employed in quantities which provide a molar ratioof (C-2):(C-1) of from about 0.1:1 to about 10:1; (3) excess X:Al ratioof from about 0.0005:1 to about 10:1; and (4) an Al:Ti atomic ratio offrom about 0.1:1 to about 2000:1.
 11. A process of claim 10 wherein(1)in component (A),(a) R" has from 1 to about 10 carbon atoms; (b) M isaluminum; and (c) x has a value from 0.001 to about 5; (2) in component(B),(a) M is aluminum; (b) R' is hydrogen or a tertiary butyl group; (c)X is chlorine; and (d) R and R' independently have from 1 to about 10carbon atoms; (3) in component (C-1),(a) R has from about 1 to about 10carbon atoms; and (b) X is chlorine; (4) in component (C-2)(a) A hasfrom 1 to about 4 carbon atoms; (b) when R is a hydroxyl substitutedhydrocarbyl or a hydroxyl substituted hydrocarbyloxy group, it has from1 to about 10 carbon atoms; and (c) when R' is a hydrocarbyl group or ahydrocarbyloxy group, it has from about 1 to about 10 carbon atoms; (5)in component (D),(a) M is aluminum; (b) R has from 1 to about 10 carbonatoms;and (c) X is chlorine; and (6) the components are employed inquantities so as to provide the following ratios:(a) a Mg:Ti atomicratio of from about 2:1 to about 100:1; (b) components (C-1) and (C-2)are employed in quantities which provide a molar ratio of (C-2):(C-1) offrom about 1:1 to about 5:1; (c) an excess X to Al ratio of from about0.002:1 to about 2:1; and (d) an Al:Ti atomic ratio of from about 0.5:1to about 200:1.
 12. A process of claim 11 whereinin component (C-1),each R has from about 2 to about 4 carbon atoms.
 13. A process of claim12 wherein the components are employed in quantities so as to providethe following ratios:(a) a Mg:Ti atomic ratio of from about 5:1 to about50:1; (b) in component (C-2)(i) n has a value of 1; (ii) A is amethylene group; and (iii) each R is independently hydrogen, a methylgroup or a phenyl group; (C) components (C-1) and (C-2) are employed inquantities which provide a molar ratio of (C-2):(C-1) of from about 1:1to about 2:1; (d) an excess X to Al ratio of from about 0.01:1 to about1.4:1; and (e) an Al:Ti atomic ratio of from about 1:1 to about 75:1.14. A process of claims 11, 12 or 13 wherein the components are added inthe order selected from(A) A, B, ((C-1) and (C-2), prereacted), D (ifrequired); (B) A, B, D (if required), ((C-1) and (C-2), prereacted); (C)(A and B, prereacted), ((C-1) and (C-2), prereacted), D (if required);(D) (A and B, prereacted), D (if required), ((C-1) and (C-2),prereacted); or (E) (A, B, and D (if required), prereacted), ((C-1) and(C-2), prereacted).
 15. A process of claims 11, 12 or 13 whereincomponent (C-1) is tetraiisopropoxy titanium, tetra-n-butoxy titanium,titanium tetrachloride or a mixture thereof.
 16. A process of claim 14wherein component (C-1) is tetraiisopropoxy titanium, tetra-n-butoxytitanium, titanium tetrachloride or a mixture thereof.
 17. A process ofclaims 11, 12 or 13 wherein ethylene or a mixture of ethylene and atleast one α-olefin having from 2 to about 10 carbon atoms ispolymerized.
 18. A process of claim 17 wherein ethylene or a mixture ofethylene and at least one of butene-1, hexene-1 or octene-1 ispolymerized.
 19. A process of claim 14 wherein ethylene or a mixture ofethylene and at least one α-olefin having from 2 to about 10 carbonatoms is polymerized.
 20. A process of claim 19 wherein ethylene or amixture of ethylene and at least one of butene-1, hexene-1 or octene-1is polymerized.
 21. A process of claim 15 wherein wherein ethylene or amixture of ethylene and at least one α-olefin having from 2 to about 10carbon atoms is polymerized.
 22. A process of claim 21 wherein ethyleneor a mixture of ethylene and at least one of butene-1, hexene-1 oroctene-1 is polymerized.
 23. A process of claim 16 wherein ethylene or amixture of ethylene and at least one α-olefin having from 2 to about 10carbon atoms is polymerized.
 24. A process of claim 23 wherein ethyleneor a mixture of ethylene and at least one of butene-1, hexene-1 oroctene-1 is polymerized.